Catalytic conversion

ABSTRACT

A method for increasing the total amount of lattice metal in the framework of a particular porous inorganic crystalline composition, its conversion to hydrogen or hydronium form and use thereof as a catalyst component having enhanced catalytic activity for conversion of oxygenates to hydrocarbons is provided.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.493,192, filed May 10, 1983, now U.S. Pat. No. 4,576,805, which is acontinuation-in-part of application Ser. No. 412,362, filed Aug. 27,1982, now abandoned, which is a continuation-in-part of application Ser.No. 333,369, filed Dec. 22, 1981, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to use of a catalyst component prepared by amethod for increasing the total amount of lattice metal in the frameworkof a particular porous inorganic crystalline composition comprising 98mole percent or more SiO₂ and 2 mole percent or less oxides of at leastone initial lattice metal selected from those of Groups IIIB, IVB, VB,VIB, VIIB, VIII, IIIA, IVA and VA of the Periodic Table of the Elements.The preparation method comprises contacting the crystalline compositionwith a particular volatile compound comprising at least one metal to becoordinated in the framework of said crystalline composition, wherebythe total amount of lattice metal subsequent to the contacting isgreater than the amount of the initial lattice metal prior to thecontacting. The volatile compound for use in the catalyst componentpreparation method comprising the metal for lattice incorporation musthave a radius ratio of less than about 0.6 and a size and shape whichwould permit it to enter the pores of the crystalline composition at thecontacting temperature.

The volatile compound contacted inorganic crystalline composition maythen be converted to the hydrogen or hydronium form and used as acatalyst component for conversion of organic compounds. Moreparticularly, oxygenates such as alcohols, carbonyls and ethers areconverted to hydrocarbons over catalyst comprising the catalystcomponent prepared by the subject method.

2. Description of Prior Art

High silica-containing zeolites are well known in the art and it isgenerally accepted that the ion exchange capacity of the crystallinealuminosilicate is directly dependent on its aluminum content. Thus, forexample, the more aluminum there is in a crystalline structure, the morecations are required to balance the electronegativity thereof, and whensuch cations are of the acidic type such as hydrogen, they imparttremendous catalytic activity to the crystalline material. On the otherhand, high silica-containing zeolites having little or substantially noaluminum, have many important properties and characteristics and a highdegree of structural stability such that they have become candidates foruse in various processes including catalytic processes. Materials ofthis type are known in the art and include high silica-containingaluminosilicates such as ZSM-5 (U.S. Pat. No. 3,702,886), ZSM-11 (U.S.Pat. No. 3,709,979), and zeolite ZSM-12 (U.S. Pat. No. 3,832,449) tomention a few.

The silica-to-alumina mole ratio of a given zeolite is often variable;for example, zeolite X can be synthesized with a silica-to-alumina ratioof from 2 to 3; zeolite Y from 3 to about 6. In some zeolites, the upperlimit of silica-to-alumina mole ratio is virtually unbounded. ZeoliteZSM-5 is one such material wherein the silica-to-alumina ratio is atleast 5. U.S. Pat. No. 3,941,871 discloses a crystalline metalorganosilicate essentially free of aluminum and exhibiting an x-raydiffraction pattern characteristic of ZSM-5. U.S. Pat. Nos. 4,061,724;4,073,865 and 4,104,294 describe microporous crystalline silicas orsilicates wherein the aluminum content present is at low levels.

Because of the extremely low aluminum content of these highsilica-containing zeolites, their ion exchange capacity is not as greatas materials with a higher aluminum content. For instance, thecrystalline compositions to be treated hereby will have ion exchangecapacity of less than about 0.7 meq/gram, whereas zeolite Y will exhibitan ion exchange capacity of from about 4.32 to about 7.1 meq/gram.Therefore, when the high silica materials are contacted with an acidicsolution and thereafter are processed in a conventional manner, they arenot as catalytically active as their higher aluminum-containingcounterparts.

The novel method of this invention permits the preparation of certainhigh silica-containing materials which have all the desirable propertiesinherently possessed by such high silica materials and, yet, have acatalytic activity which heretofore has only been possible to beachieved by materials having a higher aluminum content in their "assynthesized" form.

It is noted that U.S. Pat. Nos. 3,354,078 and 3,644,220 relate totreating certain crystalline aluminosilicates with volatile metalhalides. Neither of these latter patents are, however, concerned withtreatment of crystalline materials having a high silica/alumina moleratio and exhibiting a low cation exchange capacity of less than about0.7 meq/gram. In fact, the methods of these latter patents arecritically dependent on the presence of exchangeable cations or exchangecapacity in the crystalline aluminosilicate. Also, the latter patentsrelate to ion exchange of the aluminosilicates having exchangeablecations. The present method relies, instead, upon incorporation ofcertain elements into a framework.

A number of U.S. patents teach heteroatom feed conversion. Examples ofthese are U.S. Pat. Nos. 3,894,104, 3,894,106, 3,894,107, 3,899,544,3,965,205, 4,046,825, 4,156,698 and 4,311,865. Methanol is converted togasoline in U.S. Pat. Nos. 4,302,619, 3,928,483 and 4,058,576 asexamples. Methanol is converted to olefins and/or aromatics in, forexample, U.S. Pat. Nos. 3,911,041, 4,025,571, 4,025,572, 4,025,575 and4,049,735.

SUMMARY OF THE INVENTION

The present invention relates to use of a catalyst component prepared bya novel method for increasing the total amount of lattice metal in theframework of a porous inorganic crystalline composition comprising 98mole percent or more SiO₂ and 2 mole percent or less oxides of at leastone initial lattice metal selected from those of Groups IIIB (eg. Sc andY), IVB (eg. Ti, Zr and Hf), VB (eg. V), VIB (eg. Cr), VIIB (eg. Mn),VIII (eg. Fe, Co and Rh), IIIA (eg. B, Al and Ga), IVA (eg. Ge) and VA(eg. Sb) of the Periodic Table of the Elements and having an anhydrousanionic framework molar composition expressed by the formula

    (1-x)SiO.sub.2 :(x)MO.sub.n/2

wherein x is less than or equal to 0.02, M is said initial lattice metaland n is the valence of M. The initial lattice metal M may be acombination of metals such as, for example, B and Ga, Co and Al, Co andCr, Co and Fe, Co and Rh, Fe and Al, Rh and Al, and B and Al. Thecatalyst component preparation method comprises contacting saidcrystalline composition at a temperature of from about 100° C. to about850° C. with a volatile compound comprising at least one metal to becoordinated in the framework of said crystalline composition for a timesufficient to increase the total amount of lattice metal in theframework of said crystalline composition whereby said total amount isgreater than the amount of said initial lattice metal prior to saidcontacting. The volatile compound comprising said metal must have aradius ratio of less than about 0.6 and a size and shape which willpermit it to enter the pores of said crystalline composition at thecontacting temperature.

The volatile compound contacted inorganic crystalline composition isthen converted to the hydrogen or hydronium form.

This application is a continuation-in-part of application Ser. No.493,192, filed May 10, 1983, which is a continuation-in-part ofapplication Ser. No. 412,362, filed Aug. 27, 1982, which is acontinuation-in-part of application Ser. No. 333,369, filed Dec. 22,1981, the entire contents of each being incorporated herein byreference.

DESCRIPTION OF THE DRAWINGS

FIG. 1 of the drawings is the solid-state MASNMR spectrum of aluminum ina zeolite ZSM-5 having a silica/alumina mole ratio of 70.

FIG. 2 of the drawings is the solid-state MASNMR spectrum of aluminum ina zeolite ZSM-5 having a silica/alumina mole ratio of 26,000, i.e. thecrystalline composition of Example 1, hereinafter presented.

FIG. 3 of the drawings is the solid-state MASNMR spectrum of aluminum inthe zeolite used for the FIG. 2 spectrum which has been treated by thepresent method (Example 2, hereinafter presented).

These Figures are discussed in detail in Example 19, hereinafter.

DESCRIPTION OF SPECIFIC EMBODIMENTS

The expression "high silica-containing crystalline material" is intendedto define a crystalline structure which comprises 98 mole percent ormore SiO₂ and 2 mole percent or less oxides of at least one initiallattice metal selected from those of Groups IIIB, IVB, VB, VIB, VIIB,VIII, IIIA, IVA, and VA of the Periodic Table of the Elements andcombinations thereof and having an anhydrous anionic framework molarcomposition expressed by the formula

    (1-x)SiO.sub.2 :(x)MO.sub.n/2

wherein x is less than or equal to 0.02, M is said initial lattice metaland n is the valance of M. M may be, for example, scanadium, yttrium,titanium, zirconium, hafnium, vanadium, chromium, manganese, iron,cobalt, rhodium, boron, aluminum, gallium, germanium, antimony orcombinations thereof such as boron-aluminum, chromium-aluminum andiron-aluminum. The silica/initial lattice metal (M) oxide mole ratio maylikely be greater than about 100, or greater than about 500, or as closeto infinity as practically possible for the crystalline composition tobe treated hereby. When M is aluminum, the silica/alumina mole ratio ofthis crystalline material may be greater than about 100, or greater thanabout 500, or up to about infinity or as reasonably close to infinity aspractically possible. This latter group of highly siliceous materials isexemplified by U.S. Pat. Nos. 3,941,871; 4,061,724; 4,073,865 and4,104,294 wherein the materials are prepared from reaction solutionswhich involve no deliberate addition of aluminum. However, tracequantities of aluminum are usually present due to the impurity of thereaction solutions. It is to be understood that the expression " highsilica-containing crystalline material" also specifically includes thosematerials which have other initial lattice metals associated therewith,such as when M comprises boron, iron, chromium, etc. Thus, a requirementwith regard to the starting materials utilized in the novel process ofthis invention is that they have a silica-to-initial lattice metal oxidemole ratio greater than about 49 (irrespective of what initial latticemetals are present in the crystal structure). The expression alsoincludes crystalline materials which originally contained sufficientinitial lattice metal, eg. aluminum, to have a silica-to-initial latticemetal oxide (eg. alumina) mole ratio less than 49, but which weredemetalized, eg. dealuminized, to have such ratio above 49.

The high silica materials for advantageous treatment by the presentmethod are those having virtually no exchange capacity, i.e. a totalcation exchange capacity of less than about 0.7 meq/gram of material,and most advantageously less than about 0.1 meq/gram. An observabletotal cation exchange capacity of 0 meq/gram of the high silica materialwill be acceptable. It is noted that, by way of comparison, the totalcation exchange capacity of synthetic faujasite, such as zeolite Y,having a silica/alumina mole ratio of 5.6, on the same basis is about4.56 meq/gram.

The new catalyst component preparation method disclosed herein isdifferent in kind from ion exchange. Those skilled in the art willrecognize upon viewing the results herein presented that the presentmethod does not require the presence of exchangeable cations associatedwith the crystalline composition starting material, as ion exchangeclearly does. A crystalline zeolite structure with negligible ionexchange capacity, ie. the starting material for the present method, cannow be activated or metallated and the activated or metallated crystalshows enhanced exchange capacity, and in the case of an aluminimactivated, ie. aluminum incorporated, material when in the hydrogenform, the resultant crystal shows enhanced catalytic activity forn-hexane cracking as measured by the Alpha Test, hereafter defined.

Ion exchange, i.e., replacement of exchangeable cations of a crystallinecomposition with other cations by the methods taught or suggested inU.S. Pat. Nos. 3,354,078 and 3,644,220, and metal incorporation into acrystalline composition structure are competing mechanisms when thecrystal is contacted with a solution containing metal ions. Thisphenomenon was recognized and utilized in the present method in that asthe silica/initial lattice metal, eg. aluminum, oxide mole ratioincreases to a high value, ion exchange capacity of that materialdiminishes and ion exchange subsides to the flourishing benefit of metalincorporation under the conditions hereof. This is evident for theexamples hereinafter presented.

The starting materials utilized in the catalyst component preparationmethod may be synthesized from reaction mixtures containing various ionsources, including bulky ion sources. It is necessary that the volatileinorganic reagent have access to the intracrystalline volume or space ofthe crystalline material being treated, and, while not wishing to bebound by any theory of operation, it is though that use of a bulky ionsource in synthesis of certain starting crystalline materials may aid ingenerating such materials having larger intracrystalline space and poreopenings, thereby providing greater access for the volatile inorganicreagent.

Bulky ion sources useful in the synthesis of some starting material tobe utilized herein include, but are not limited to, onium compounds andcompounds containing multiple cationic centers. Onium compounds arethose having the following formula:

    R.sub.4 M.sup.+ X.sup.-

wherein R is alkyl of from 1 to 20 carbon atoms, heteroalkyl of from 1to 20 carbon atoms, aryl, heteroaryl, cycloalkyl of from 3 to 6 carbonatoms, cycloheteroalkyl of from 3 to 6 carbon atoms, or combinationsthereof; M is a quadricoordinate element (e.g. nitrogen, phosphorus,arsenic, antimony or bismuth) or a heteroatom (e.g. N, O, S, Se, P, As,etc.) in an alicyclic, heteroalicyclic or heteroaromatic structure; andX is an anion (e.g. fluoride, chloride, bromide, iodide, hydroxide,acetate, sulfate, carboxylate, etc.). When M is a heteroatom in analicyclic, heteroalicyclic or heteroaromatic structure, such structuremay be, as non-limiting examples, ##STR1## wherein R' is alkyl of from 1to 20 carbon atoms, heteroalkyl of from 1 to 20 carbon atoms, aryl,heteroaryl, cycloalkyl of from 3 to 6 carbon atoms or cycloheteroalkylof from 3 to 6 carbon atoms.

Compounds containing multiple cationic centers include those having theformula:

    [(R).sub.3 M.sup.+ (Z).sub.n M.sup.+ (R).sub.3 ](X.sup.-).sub.2

wherein R, M and X are as above defined, Z is a bridging member selectedfrom the group consisting of alkyl of from 1 to 20 carbon atoms, alkenylof from 2 to 20 carbon atoms, aryl, heteroalkyl of from 1 to 20 carbonatoms, heteroalkenyl of from 2 to 20 carbon atoms and heteroaryl, and nis a number of from 1 to about 50. Non-limiting examples of suchmultiple cationic center containing compounds include: ##STR2##

The size of the volatile compound should be comparable to or smallerthan the critical pore dimension of the crystalline composition in orderto enter into the pores of the crystal and be in a location suitable forlattice incorporation. Therefore, it is believed that the volatilecompound must have a critical size and shape at the contactingtemperature comparable to or less than the critical pore dimension ofthe crystal at that temperature. The "critical pore dimension" is thepore dimension which would limit sorption of the volatile compound atthe contacting temperature. It is the kinetic diameter of a circularpore and, it is about the minor axis size of an elliptical pore.However, it is not inconceivable that a bulky volatile compound reagentmay, upon contact with the exterior surface of the crystallinecomposition, be transformed into smaller species which enter the poreswith greater facility. A putative example may be Al₂ Cl₆ (gas)⃡2AlCl₃(sorbate).

The catalyst component preparation method is simple and easy to carryout although the results therefrom are dramatic. It is carried out bysubjecting a calcined high silica crystalline material satisfying theabove description to contact with a volatile compound having a radiusratio of less than about 0.6, preferably from greater than about 0.1 toless than about 0.6, and a size and shape which would permit it to enterthe pores of the high silica crystalline material, at a temperature offrom about 100° C. to about 850° C., preferably from about 100° C. toabout 500° C.

The volatile compound contacted material will then be converted to theacid form, i.e. the hydrogen or hydronium form. This may be accomplishedby hydrolysis followed by calcination, by contact with an ammonium saltor acid solution followed by calcination or, if the crystalline materialcontains hydrogen precursor material by way of its synthesis, bycalcination.

Without wishing to be bound by any theory of operation, it is believedthat the central atom of the volatile compound, e.g. aluminum inaluminum chloride, actually enters the high silica crystalline materialframework by coordination, tetrahedral or otherwise, with latticedefects. Central to this hypothesis is the assumed presence of latticedefects or "hydroxyl nests" (R. M. Barrer et al, Can. J. Chem. 42, 1964,p. 1481) which can accommodate the reactant volatile compound centralatom.

The volatile compound contacting step may be accomplished by admixtureof the volatile compound reagent with an inert gas such as nitrogen orhelium at temperatures ranging from about 100° C. to about 850° C.,preferably from about 100° C. to about 500° C. The amount of reagentcompound vapor which is utilized is not narrowly critical but usuallyfrom about 0.2 to about 2 grams of volatile compound are used per gramof high silica crystalline starting material. In any event, thecontacting is conducted in an anhydrous system, eg. the vapors of thereagent compound are dry.

The volatile compound for use herein will exhibit a radius ratio of lessthan about 0.6, preferably from greater than about 0.1 to less thanabout 0.6. The term "radius ratio" is defined by L. Pauling in TheNature of the Chemical Bond, Third Edition, Cornell University Press,1960, Chapter 13, pages 505 et seq, incorporated herein by reference asto definition of radius ratio, for inorganic compounds. The radius ratiofor the volatile compound used herein is: ##EQU1##

The metal of the volatile compound must be small enough in ionic stateto easily fit into the tetrahedral lattice location. It is believed thata compound having a radius ratio of less than 0.6 will provide the metalin its ionic state in a size which will easily fit. Therefore, avolatile compound having a radius ratio of less than 0.6 will be usefulfor increasing the content of coordinated, tetrahedrally or otherwise,lattice metal in the framework of an inorganic porous crystallinecomposition satisfying the above description, such as ZSM-5.

The crystal ionic radii of elements are listed in the CRC Handbook ofChemistry and Physics, 61st Edition, CRC Press, Inc., 1980, pages F-216and F-217, said listing incorporated herein by reference. In determiningthe radius ratio of a particular compound, it is necessary to usecrystal ionic radii of the central atom therein (e.g. aluminum inaluminum chloride) and the oxygen anion (e.g. O⁻²) which have beenmeasured by the same method. Non-limiting examples of inorganiccompounds satisfying the radius ratio limitation of 0.6, along withtheir radius ratio in parenthesis, include the following:

AlBr₃ (0.386)

AlCl₃ (0.386)

BCl₃ (0.174)

FeCl₃ (0.485)

CrO₂ Cl₂ (0.394)

PCl₃ (0.333)

TiCl₄ (0.515)

SnCl₄ (0.538)

GaCl₃ (0.470)

Inorganic compounds not useful in the present method since their radiusratios fail to satisfy the radiaus ratio limitation of 0.6 include, forexample, UF₆ (0.606), SnCl₂ (0.704), CrCl₂ (0.674), TiCl₂ (0.712), SrCl₂(0.848) and CeCl₃ (0.783).

The compound for use herein will also be one which is volatile withinthe temperature range of from about 100° C. to about 850° C. It willlikely have a vapor pressure of greater than about 10 mm at atemperature of about 400° C.

Non-limiting examples of compounds satisfying the 0.6 radius ratio andvolatility limitations hereof include inorganic halides, eg. chloridesand bromides, having a central atom selected from the group consistingof Al⁺³, B⁺³, Be⁺², Co⁺², Cr⁶, Fe⁺³, Ga⁺³, Ta⁺⁵, Mn⁺⁴, Mo⁺⁶, P⁺³, Sb⁺³,Sn⁺⁴, Ti⁺⁴, V⁺⁵, W⁺⁶ and Zr⁺⁴.

The conversion of the volatile compound contacted material to acid form,i.e. hydrogen or hydronium form, may be accomplished in one of severalways. It may be accomplished by contact with an ammonium salt or acidsolution followed by calcination at a temperature of from about 200° C.to about 600° C. in an inert atmosphere of air, nitrogen, etc. atsubatmospheric, atmospheric or superatmospheric pressure for from about1 minute to about 48 hours. The ammonium salt solution and acid solutionmay be aqueous in concentrations of from about 0.01N to about 1Nammonium salt and from about 0.01N to about 0.5N acid. The contact timewill be from about 1 hour to about 20 hours at a temperature of fromambient to about 100° C. The ammonium salt used is not narrowly criticaland will normally be an inorganic salt such as ammonium nitrate,ammonium sulfate, ammonium chloride, etc. The acid used will normally bean organic or inorganic acid such as acetic acid, hydrochloric acid,nitric acid, etc.

The conversion of the volatile compound contacted material to acid formmay also be accomplished by hydrolysis, such as by contact with water ata temperature of from about 20° C. to about 550° C., followed bycalcination as above. When the hydrolyzing temperature is below 100° C.at atmospheric pressure, liquid water may be used. When the boilingpoint of water is exceeded, such as when the hydrolyzing temperatureexceeds 100° C. at atmospheric pressure, the crystalline material may bepurged with water saturated gas, e.g. helium. Of course, hydrolysis andaluminum salt solution or acid solution contacting may be conductedsimultaneously when the salt or acid solution is aqueous.

The conversion to acid form may also be accomplished if the crystallinematerial was synthesized with a hydrogen precursor reaction mixturecomponent present, by calcination of the volatile compound contactedmaterial at a temperature of from about 200° C. to about 600° C. in aninert atmosphere of air, nitrogen, etc. at subatmospheric, atmosphericor superatmospheric pressure for from about 1 minute to about 48 hours.

Of the high silica zeolite materials advantageously treated inaccordance herewith, zeolites having the structure of ZSM-5, ZSM-11,ZSM-5/ZSM-11 intermediate, ZSM-48, dealuminized ZSM-20, dealuminizedzeolite Y or zeolite Beta are particularly noted. ZSM-5 is described inU.S. Pat. Nos. 3,702,886 and Re. 29,948, the entire contents of eachbeing hereby incorporated by reference herein. ZSM-11 is described inU.S. Pat. No. 3,709,979, the entire teaching of which is incorporatedherein by reference. ZSM-5/ZSM-11 intermediate zeolite is described inU.S. Pat. No. 4,229,424, incorporated herein in its entirety byreference.

ZSM-48 is described in U.S. Pat. No. 4,375,573, the entire contents ofwhich is incorporated herein by reference. Zeolite Beta is described inU.S. Pat. Nos. 3,308,069 and Re. 28,341, the entire contents of eachbeing incorporated herein by reference. Preparing said zeolite Beta witha silica/alumina mole ratio above the 100 to 150 maximum specified inU.S. Pat. Nos. 3,308,069 and Re. 28,341 may be accomplished byextraction with acid.

Zeolite Y can be synthesized only in forms which have silica/aluminaratios up to about 5 and in order to achieve higher ratios, resort maybe made to various techniques to remove structural aluminum so as toobtain a more highly siliceous zeolite. Zeolite ZSM-20 may be directlysynthesized with silica/alumina ratios of 7 or higher, typically in therange of 7 to 10, as described in U.S. Pat. Nos. 3,972,983 and4,021,331, the entire contents of each being incorporated herein byreference.

A number of different methods are known for increasing the structuralsilica/alumina mole ratio of various zeolites such as ZSM-20, Beta andY. Many of these methods rely upon the removal of aluminum from thestructural framework of the zeolite by chemical agents appropriate tothis end. A considerable amount of work on the preparation of aluminumdeficient faujasites has been performed and is reviewed in Advances inChemistry Series No. 121, Molecular Sieves, G. T. Kerr, AmericanChemical Society, 1973. Specific methods for preparing dealuminizedzeolites are described in the following, which are incorporated byreference herein for details of the methods: Catalysis by Zeolites(International Symposium on Zeolites, Lyon, Sept. 9-11, 1980), ElsevierScientific Publishing Co., Amsterdam, 1980 (dealuminization of zeolite Ywith silicon tetrachloride); U.S. Pat. No. 3,442,795 and G.B. Pat. No.1,058,188 (hydrolysis and removal of aluminum by chelation); G.B. Pat.No. 1,061,847 (acid extraction of aluminum); U.S. Pat. No. 3,493,519(aluminum removal by steaming and chelation); U.S. Pat. No. 3,591,488(aluminum removal by steaming); U.S. Pat. No. 4,273,753 (dealuminizationby silicon halides and oxyhalides); U.S. Pat. No. 3,691,099 (aluminumextraction with acid); U.S. Pat. No. 4,093,560 (dealuminization bytreatment with salts); U.S. Pat. No. 3,937,791 (aluminum removal withCr(III) solutions); U.S. Pat. No. 3,506,400 (steaming followed bychelation); U.S. Pat. No. 3,640,681 (extraction of aluminum withacetylacetonate followed by dehydroxylation); U.S. Pat. No. 3,836,561(removal of aluminum with acid); Japan Pat. No. 53,101,003 (treatmentwith EDTA or other materials to remove aluminum) and J. Catalysis 54 295(1978) (hydrothermal treatment followed by acid extraction).

Highly siliceous forms of zeolite having the structure of zeolite Y maybe prepared by steaming or by acid extraction of structural aluminum (orboth) but because zeolite Y in its normal, as-synthesized condition, isunstable to acid, it must first be converted to an acid-stable form.Methods for doing this are known and one of the most common forms ofacid-resistant zeolite Y is known as "Ultrastable Y" (USY); it isdescribed in U.S. Pat. Nos. 3,293,192 and 3,402,996 and the publication,Society of Chemical Engineering (London) Monograph Molecular Sieves,page 186 (1968) by C. V. McDaniel and P. K. Maher, and incorporationherein by reference is made to these for details of the zeolite and itspreparation. In general, "ultrastable" refers to Y-type zeolite which ishighly resistant to degradation of crystallinity by high temperature andsteam treatment and is characterized by a R₂ O content (wherein R is Na,K or any other alkali metal ion) of less than 4 weight percent,preferably less than 1 weight percent, and a unit cell size less than24.5 Angstroms and a silica/alumina mole ratio in the range of 3.5 to 7or higher. The ultrastable form of Y-type zeolite is obtained primarilyby a substantial reduction of the alkali metal ions and the unit cellsize. The ultrastable zeolite is identified both by the smaller unitcell and the low alkali metal content in the crystal structure.

Other specific methods for increasing the silica/alumina mole ratio ofzeolite Y by acid extraction are described in U.S. Pat. Nos. 4,218,307,3,591,488 and 3,691,099, incorporated herein by reference for details ofthese methods.

Zeolite ZSM-20 may be converted to more highly siliceous forms by aprocess similar to that used for zeolite Y. First, the zeolite may beconverted to an "ultrastable" form which is then dealuminized by acidextraction. The conversion to the ultrastable form may suitably becarried out by the same sequence of steps used for preparing ultrastableY. The zeolite is successively base-exchanged to the ammonium form andcalcined, normally at temperatures above 700° C. The calcination shouldbe carried out in a deep bed in order to impede removal of gaseousproducts. Acid extraction of the "ultrastable" ZSM-20 may be effected inthe same way as mentioned above for zeolite Beta.

The feedstock to the present process may comprise lower aliphaticalcohols, carbonyls, ethers or mixtures thereof. Feedstock alcohols willbe aliphatic alcohols of from 1 to about 6 carbon atoms, preferably from1 to 3 carbon atoms, e.g., methanol and ethanol. Feedstock carbonylswill be lower aliphatic carbonyls, such as, for example, acetone.Feedstock ethers will be lower aliphatic ethers of up to about 6 carbonatoms, e.g., from 2 to about 6 carbon atoms, such as dimethylether,n-propyl ether, p-dioxane, trioxane and hexose.

The product of this process when alcohols, carbonyls or ethers areconverted will be predominantly hydrocarbons including olefins of from 2to 5 or more carbon atoms with C₂ olefins usually less than about 10% ofthe total and C₅ ⁺ olefins usually less than about 15% of the total.Aromatic hydrocarbons, such as durene, are also produced. C₃ and C₄olefins are desired chemical products, and C₅ ⁺ products are valuable asgasoline components.

Reaction conditions for the conversion of alcohols, carbonyls, ethers ormixtures thereof to hydrocarbons, e.g., olefins, and hydrocarbonsincluding aromatics, e.g., gasoline components, include a temperature offrom about 275° C. to about 600° C., a pressure of from about 0.5atmosphere to about 50 atmospheres and a liquid hourly space velocity offrom about 0.5 hr⁻¹ to about 100 hr⁻¹.

In practicing a particularly desired chemical conversion process, it maybe useful to incorporate the above-described activity enhancedcrystalline material with a matrix comprising another material resistantto the temperature and other conditions employed in the process. Suchmatrix material is useful as a binder and imparts greater resistance tothe catalyst for the severe temperature, pressure and reactant feedstream velocity conditions encountered in, for example, many crackingprocesses.

Useful matrix materials include both synthetic and naturally occurringsubstances, as well as inorganic materials such as clay, silica and/ormetal oxides. The latter may be either naturally occurring or in theform of gelatinous precipitates or gels including mixtures of silica andmetal oxides. Naturally occurring clays which can be composited with thezeolite include those of the montmorillonite and kaolin families, whichfamilies include the sub-bentonites and the kaolins commonly known asDixie, McNamee, Georgia and Florida clays or others in which the mainmineral constituent is halloysite, kaolinite, dickite, nacrite oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, acid treatment or chemicalmodification.

In addition to the foregoing materials, the zeolites employed herein maybe composited with a porous matrix material such as alumina,silica-alumina, silica-magnesia, silica-zirconia, silica-thoria,silica-beryllia, and silica-titania, as well as ternary compositions,such as silica-alumina-thoria, silica-alumina-zirconia,silica-alumina-magnesia and silica-magnesia-zirconia. The matrix may bein the form of a cogel. The relative proportions of activity enhancedzeolite component and inorganic oxide gel matrix, on an anhydrous basis,may vary widely with the zeolite content ranging from between about 1 toabout 99 percent by weight and more usually in the range of about 5 toabout 80 percent by weight of the dry composite.

The following examples will illustrate the novel process of the presentinvention.

EXAMPLE 1

A high silica-containing ZSM-5 prepared as in U.S. Pat. No. 3,702,886from a reaction mixture containing tetraalkylammonium ions and having asilica/alumina mole ratio of about 26,0000:1 was treated with 1N NH₄NO₃, washed with water and treated with 0.5N HNO₃ and then washed withwater again and calcined in air for 30 minutes at 538° C. The finalproduct was a HNaZSM-5 comprising 92 ppm bulk alumina and 210 ppmsodium, having a total cation exchange capacity evaluated in terms ofammonia desorption in meq N/gram of material by way of thermogravimetricanalysis of less than 0.008 meq/gram.

EXAMPLE 2

A 5.5 gram sample of the calcined crystalline material from Example 1was placed in the center of a 1.8 cm I.D.×25 cm vycor tube. One end ofthe tube was filled with anhydrous inorganic halide (about 3.5 grams ofAlCl₃) having a radius ratio of 0.386. A 4-way stop-cock was used todirect a helium flow to either end, through the tube and to vent. A pipefurnace long enough to cover 2/3 of the tube length was used as a heatsource. The crystalline material was heated to 375° C. with He flowthrough the inorganic halide, unused inorganic halide collecting on thecold downstream end. The critical size and shape of the anhydrous AlCl₃at 375° C. is such that it enters the pores of the crystalline materialat that temperature. The flow was reversed after 1 hour and the furnacewas moved to cover the condensed inorganic halide. Cold air was used tochill the down stream end. The system was subjected to 12 hourly flowchanges or cycles. At the end of every third cycle, the temperature wasraised to 550° C. for 30 minutes. The product was exchanged twice with1N NH₄ NO₃ and calcined overnight in air at 538° C.

EXAMPLE 3

A 0.5 gram quantity of the calcined crystalline material from Example 1was exchanged twice with 1N NH₄ NO₃ and calcined in air for 16 hours at538° C.

EXAMPLE 4

The ammonium exchanged material from Example 3 and fully treatedmaterial from Example 2 were examined for total cation exchange capacityand catalytic activity. These values were also determined for thematerial from Example 1 for comparison purposes. The exchange capacitywas evaluated in terms of ammonia desorption in meqN/gram of material byway of thermogravimetric analysis. The catalytic acivity was evaluatedin terms of Alpha Value which is an approximate indication of thecatalytic cracking activity of the catalyst compared to a standardcatalyst and it gives the relative rate constant (rate of normal hexaneconversion per volume of catalyst per unit time). It is based on theactivity of the highly active silica-alumina cracking catalyst taken asan Alpha of 1 (rate constant=0.016). The Alpha Test is described in U.S.Pat. No. 3,354,078 and in The Journal of Catalysts, Vol. IV, pp. 522-529(August 1965), the contents of each being incorporated herein byreference as to said description. The relationship of Alpha Value to theintrinsic rate constants of other acid-catalyzed reactions is detailedin Nature, Vol. 309, pp. 589-591, June 14, 1984, incorporated herein byreference as to that detail.

The results of these examinations are listed below. The improvement byway of the present method is evident, showing activation of a materialhaving no appreciable cation exchangeability. The observed increase inexchange capacity for the material treated by the present method isevidence of aluminum incorporation. The substantial enhancement in Alphaactivity suggests that the aluminum of the inorganic halide has enteredthe crystalline material framework as tetrahedral aluminum.

    ______________________________________                                        Crystalline                                                                   Material    Example 1  Example 2  Example 3                                   ______________________________________                                        Cation Exchange                                                                           less than  0.0564     less than                                   Capacity, meq/gram                                                                        0.008                 0.008                                       Alpha Value about 0.1  100        about 0.15                                  SiO.sub.2 /Al.sub.2 O.sub.3, molar                                                        26,000     less than 590                                                                            26,000                                                             (estimated)                                            ______________________________________                                    

EXAMPLE 5

(A) A high silica-containing ZSM-5 prepared as in U.S. Pat. No.3,702,886 from a reaction mixture containing tetraalkylammonium ions andhaving a silica-to-alumina mole ratio of about 26,000:1 (65 ppmframework alumina, 110 ppm bulk alumina and 0.23 percent sodium) wascalcined in air for 30 minutes at 538° C. This material had a totalcation exchange capacity of virtually 0 meq/gram.

(B) A high silica-containing ZSM-5 prepared as in U.S. Pat. No.3,702,886 from a reaction mixture containing tetraalkylammonium ions andhaving a silica-to-alumina mole ratio of about 600:1 was calcined for 30minutes in air at 538° C. This material had a total cation exchangecapacity of 0.055 meq/gram.

EXAMPLE 6

A vycor tube was loaded with 2 grams anhydrous AlBr₃ having a radiusratio of 0.386 and 4 grams of the product of Example 5(A), separatingthe components with a thin plug of vycor wool. A stream of helium (about100 ml/minute) was passed through the AlBr₃ and then through thecrystalline material. The temperature was increased to 100° C. for onehour and then at 5° C./minute to 370° C. The reactor tube was tiltedabout 30 degrees to retain any liquid AlBr₃ near the inlet. After 30minutes at 370° C., the reactor tube was removed, cooled, and sealed atroom temperature overnight. The reactor tube was again heated with thehelium flow to 500° C. for one hour. The critical size and shape of theanhydrous AlBr₃ at 370° C. is such that it enters the pores of thecrystalline material at that temperature.

EXAMPLE 7

An aliquot of the product of Example 6 was hydrolyzed by treating withwater at room temperature three times for 45 minutes each. The resultinghydrolyzed crystalline material was calcined in flowing air for 30minutes at 538° C.

EXAMPLE 8

An aliquot of the product of Example 6 was hydrolyzed by purging at200°-550° C. with water saturated helium (45°-50° C., 80-90 mm H₂ O) andthen calcined in flowing air from 30 minutes at 538° C.

EXAMPLE 9

An aliquot of the product of Example 6 was base-exchanged with anaqueous solution of 1N NH₄ NO₃ (3-exchanges followed by hot waterwashing). The resulting exchanged crystalline material was calcined for30 minutes at 538° C. in flowing air.

EXAMPLE 10

The product zeolites of Examples 5(A), 7, 8 and 9 were evaluated forcatalytic activity by the Alpha Test. The results of these tests arebelow:

    ______________________________________                                        Crystalline Product of                                                        Example Number   Alpha Value                                                  ______________________________________                                        5(A) (basis)     0.015                                                        7                50                                                           8                29                                                           9                71                                                           ______________________________________                                    

EXAMPLE 11

An aliquot of the product of Example 5(B) was treated with anhydrousAlBr₃ as in Example 6 except that nitrogen was used instead of heliumand the temperature was maintained at 130° C. for overnight. Theresulting crystalline material was calcined in air at 538° C. overnightand then base-exchanged with 1N NH₄ NO₃ aqueous solution. The exchangedmaterial was then calcined for 30 minutes at 538° C. in flowing air.

EXAMPLE 12

An aliquot of the product of Example 5(B) was calcined overnight in airat 538° C., then base-exchanged with an aqueous solution of 1N NH₄ NO₃,and then calcined for 30 minutes at 538° C. in flowing air. The productof this example was not contacted with the inorganic halide, i.e.aluminum bromide, as was the case for Example 11.

EXAMPLE 13

The product zeolites of Examples 11 and 12 were evaluated for catalyticactivity as in Example 10 and for structural aluminum and siliconcontents. The results are listed below:

    ______________________________________                                                        Crystalline Product of                                                        Example Number                                                                11     12                                                     ______________________________________                                        Alpha Value       15       10                                                 Aluminum Content, % wt.                                                                         1.24     0.16                                               Silicon Content, % wt.                                                                          46.45    46.77                                              ______________________________________                                    

EXAMPLE 14

In order to demonstrate relative importance of converting the inorganichalide contacted material to the hydrogen or hydronium form, a 3 gramaliquot of the high silica-containing ZSM-5 prepared in Example 5(A) wasplaced in one side of a glass reactor and 1.5 grams of anhydrous AlCl₃in the other. The materials were flushed at 100° C. with helium flowingat 50 ml/minute. The aluminum chloride was carried through the bed ofZSM-5 while heating to 200° C. at about 2° C. per minute, to 500° C. atabout 5° C. per minute and maintaining the reactor at 500° C. for 30minutes. The zeolite was placed in a clean reactor and flushed withhelium at 500° C. for 30 minutes to remove any unreacted aluminumchloride. Half the product was then hydrolyzed by standing in 100 mlwater at room temperature for two hours. It was then decanted and driedovernight at 130° C. Both halves were then calcined in air at 538° C.for 30 minutes. Both the hydrolyzed and unhydrolyzed halves were testedfor n-hexane cracking by the Alpha Test. The results of these tests arelisted below with results of the same tests for the ZSM-5 treated inaccordance herewith, i.e. Example 9, for comparison. The improvement isevident.

    ______________________________________                                        Crystalline Product of                                                        Example Number   Alpha Value                                                  ______________________________________                                        5(A) (basis)     0.015                                                        9                71                                                           14 (unhydrolyzed)                                                                              0.6                                                          14 (hydrolyzed)  32                                                           ______________________________________                                    

EXAMPLE 15

A dealuminized zeolite Y having a silica/alumina mole ratio of 278 wasprepared from NH₄ NaY with a silica-to-alumina mole ratio of 5 by aseries of NH₄ ⁺ exchange/calcinations followed by a series of acidextractions with increasing acid strength. The dealuminized zeolite Yexhibited negligible total cation exchange capacity (i.e. about 0meq/gram), and an Alpha Value of between 0.4 and 0.7. An aliquot of thedealuminized zeolite Y was treated as in Example 2 (aluminum chloridebeing the volatile compound) and tested for exchange capacity and AlphaValue as in Example 4. The final material had a total cation exchangecapacity of 0.575 meq/gram and an Alpha Value of 18.

The observed increase in exchange capacity for the dealuminized Y, aswell as the zeolite ZSM-5 of Example 2, is evidence of metal, ie.aluminum, incorporation by the present method. Again, the substantialenhancement in Alpha activity suggests that the metal has entered thezeolite framework, in this instance as tetrahedral aluminum.

In the treatment of dealuminized zeolite Y, the activity enhancement isrelatively lower than that for zeolite ZSM-5. This is believed explainedin light of the Kerr mechanism (G. T. Kerr, ACS Adv. Chem. Ser. No. 121,1974, p. 219) for ultrastabilization of dealuminized Y. According tothis mechanism, the vacancies generated by aluminum removal fromfaujasites tend to "heal" by incorporation of extra-framework Si(OH)₄.Defect sites available for tetrahedral coordination will therefore belimited in dealuminized Y. Therefore, it may be inferred from the largeenhancement in exchange capacity observed in Example 15 that asignificant fraction of the aluminum added by way of the volatilecompound is incompletely coordinated in the lattice, or possibly presentas occluded silica-alumina in the dealuminized zeolite Y. This isconsistent with the hypothesis that lattice defects are implicated inthe present method for activity enhancement of high silica crystallinematerials having negligible cation exchange capacity with inorganichalides.

EXAMPLE 16

A crystalline zeolite Beta preparation with a silica/alumina mole ratioof 176 and a cation exchange capacity of only about 0.19 meq/gram iscalcined for 30 minutes at 538° C. A 3 gram aliquot is placed in onehalf of a vycor reactor and 2 grams of ferric chloride (radius ratio of0.485) in the other. The system is heated slowly at about 2° C. perminute to 550° C. Ferric chloride has a size and shape at 550° C. suchthat it enters the pores of zeolite Beta. The reactor is tipped about15° C. from the horizontal so that flowing helium (100 ml/min) is passedthrough the molten or boiling ferric chloride, and then through thezeolite bed. The crystalline zeolite Beta is then purged at 550° C. for30 minutes and cooled. It is then exchanged with 1N NH₄ NO₃, calcined inair at 538° C. for 16 hours, and tested for catalytic activity alongwith the untreated zeolite Beta in the Alpha test. The results of thistest are below:

    ______________________________________                                        Crystalline Material                                                                            Alpha Value                                                 ______________________________________                                        Untreated Zeolite Beta                                                                          68                                                          Used in Example 16                                                            Treated Zeolite Beta                                                                            est. 85                                                     of Example 16                                                                 ______________________________________                                    

EXAMPLE 17

A crystalline "borosilicate" having the structure of zeolite Beta and asilica/alumina mole ratio of 145, a silica/boria mole ratio of 29.6 anda cation exchange capacity of approximately 0.23 meq/gram was tested inthe Alpha Test and found to have an Alpha Value of 33. An aliquot ofthis crystalline material is treated by the present method as in Example16, except that the ferric chloride is replaced with aluminum chloridehaving a radius ratio of 0.386 and a size and shape which permits itsentrance into the pores of the crystalline borosilicate at thetemperature of 550° C. The aluminum chloride contacted crystallinematerial is then exchanged with 1N NH₄ NO₃, calcined as in Example 16and tested for catalytic activity in the Alpha Test. The treatedmaterial exhibits an Alpha Value of about 300 (compared to 33 for theuntreated material).

EXAMPLE 18

A crystalline "ferrosilicate" having the structure of zeolite ZSM-5 with1.21 wt. % Fe₂ O₃, 105 ppm Al₂ O₃, the balance SiO₂, was determined tocontain approximately 24% of the Fe in framework position by ammoniasorption and temperature programmed desorption. The cation exchangecapacity of this crystalline material was less than 0.7 meq/gram. Analiquot of this material was tested in the Alpha Test and found to havean Alpha Value of 1.1. A further aliquot of this material is treated bythe present method as in Example 17 with aluminum chloride. The aluminumchloride contacted crystalline material is then exchanged and calcinedas in Example 17 and tested for catalytic activity in the Alpha Test.The treated material exhibits an Alpha Value of about 30 (compared to1.1 for the untreated material).

EXAMPLE 19

Solid state ²⁷ Al MASNMR studies were carried out to substantiate theobservations that the present method is new and different from ionexchange and to verify the hypothesis that aluminum activation herebyinvolves the insertion of Al³⁺ into framework tetrahedral positions inthe crystalline composition producing zeolite catalytic activity such asthat present in the same zeolite or other zeolites synthesized with aninitially lower SiO₂ /Al₂ O₃ mole ratio, ie. more Al³⁺ originally inframework tetrahedral positions. Solid state NMR determines from therelative resonance position the coordination and environment of anelement in a solid, such as the coordination of Al³⁺ in a zeolite or inalumina. In alumina, Al³⁺ has both tetrahedral and octahedralcoordination; the octehedral Al³⁺ resonance peak appears at 10 ppmrelative to Al³⁺ in solution and the tetrahedral Al³⁺ resonance peakappears at 74 ppm.

In zeolite ZSM-5 for example, only tetrahedral Al⁺³ is observed. TheAl³⁺ resonance peak appears at 53 ppm and its intensity is proportionalto the amount of tetrahedral Al⁺³ present. FIG. 1 shows a typical ²⁷ Alsolid state MASNMR resonance spectrum for zeolite ZSM-5 having a SiO₂/Al₂ O₃ mole rtio of 70; the Al resonance peak is at 53 ppm. FIG. 2shows the resonance spectrum for the ZSM-5 composition of Example 1having a 26,000:1 SiO₂ /Al₂ O₃ mole ratio. This spectrum was obtained ata higher sensitivity than those of FIGS. 1 and 3 in order to enhance anypotential Al resonance peak. For the same spectrometer operationalparameters, no Al resonance peak was observed (ie. at 53 ppm) because ofthe extremely low concentration of aluminum in that structure. Even withhigher sensitivity, no Al resonance peak was observed for thiscomposition. FIG. 3 shows the MASNMR spectrum of this same sample aftertreatment as in Example 2 in accordance with the present invention. TheAl resonance peak is at 53 ppm indicative of framework tetrahedralaluminum in the treated ZSM-5. These aluminum species are generated bythe present metallation procedure and their tetrahedral nature, as wellas their catalytic behavior, is consistent with aluminum insertion intothe lattice in tetrahedral framework sites. Ordinary ion exchange (e.g.as provided by the methods taught or suggested in U.S. Pat. Nos.3,354,078 and 3,644,220) would result only in an increase in theoctahedral Al resonance at about 10 ppm. The intensity of the ²⁷ AlMASNMR signal for the Al³⁺ activated sample (FIG. 3) is consistent withits catalytic activity (Alpha Value=100) relative to that of theas-synthesized 70 to 1 SiO₂ /Al₂ O₃ material (FIG. 1, Alpha Value=about170).

EXAMPLE 20

To further demonstrate the present process, a 2 gram sample of calcinedproduct from Example 9 is placed in a reactor vessel and contacted withfeedstock comprised of methanol at a liquid hourly space velocitymaintained at 1 hr⁻¹, a pressure of 1 atmosphere and a temperature of370° C. Conversion of the methanol to hydrocarbons is measured to beover about 90%. Analysis of the product hydrocarbons from thisexperiment is presented in the following TABLE, values approximate.

EXAMPLE 21

The experiment of Example 20 is repeated except with the reactiontemperature increased to 500° C. Here, approximately 99% of the methanolis converted to hydrocarbons. Analysis of the product hydrocarbons fromthis experiment is presented in the following TABLE, values approximate.

                  TABLE                                                           ______________________________________                                                            Example                                                   Product Hydrocarbons, wt. %                                                                         20     21                                               ______________________________________                                        C.sub.1               0.8    4.9                                              C.sub.2               0.1    0.6                                              C.sub.2 =             10.9   9.8                                              C.sub.3               1.4    2.4                                              C.sub.3 =             16.7   37.3                                             iC.sub.4              5.7    2.3                                              nC.sub.4              0.4    0.7                                              C.sub.4 =             11.5   18.5                                             iC.sub.5              5.4    3.3                                              nC.sub.5              0.2    0.4                                              C.sub.5 =             5.8    6.4                                              C.sub.6.sup.+ non-aromatics                                                                         28.0   5.7                                              C.sub.6 aromatics     --     0.1                                              C.sub.7 aromatics     1.0    0.9                                              C.sub.8 aromatics     4.2    2.7                                              C.sub.9 aromatics     4.6    2.3                                              C.sub.10 aromatics    3.3    1.7                                              C.sub.2 =-C.sub.5 =   44.9   72.0                                             Aromatics             13.3   7.8                                              ______________________________________                                    

What is claimed is:
 1. A process for converting a feedstock comprisingorganic compounds selected from the group consisting of alcohol,carbonyl, ether and mixtures thereof to conversion product comprisinghydrocarbon compounds which comprises contacting said feedstock atconversion conditions with a catalyst composition comprising a porousinorganic crystalline composition of enhanced cation exchange capacityprepared by a method for increasing the total amount of lattice metal inthe framework of a porous inorganic crystalline composition comprising98 mole percent or more SiO₂ and 2 mole percent or less oxides of atleast one initial lattice metal selected from those of Groups IIIB. IVB,VB, VIB, VIIB, VIII, IIIA, IVA and VA of the Periodic Table of theElements and having an anhydrous anionic framework molar compositionexpressed by the formula

    (1-x)SiO.sub.2 :(x)MO.sub.n/2

wherein x is less than or equal to 0.02, M is said initial lattice metaland n is the valance of M, which method comprises contacting saidcrystalline composition at a temperature of from about 100° C. to about850° C. with a volatile compound comprising at least one metal to becoordinated in the framework of said crystalline composition for a timesufficient to increase the total amount of lattice metal in theframework of said crystalline composition wherein said total amount isgreater than the amount of said initial lattice metal prior to saidcontacting, said volatile compound comprising said metal having a radiusratio of less than about 0.6 and a size and shape which permits saidvolatile compound to enter the pores of said crystalline composition atthe contacting temperature, converting said volatile compound contactedinorganic crystalline composition to the hydrogen or hydronium form, andrecovering said porous inorganic crystalline composition of enhancedcation exchange capacity.
 2. The process of claim 1 wherein said radiusratio is greater than about 0.1.
 3. The process of claim 1 wherein saidconversion to hydrogen or hydronium form comprises calcining saidvolatile compound contacted crystalline composition at a temperature offrom about 200° C. to about 600° C.
 4. The process of claim 1 whereinsaid conversion to hydrogen or hydronium form comprises contacting saidvolatile compound contacted crystalline composition with an aqueous acidor ammonium salt solution thereafter calcining said material at atemperature of from about 200° C. to about 600° C.
 5. The process ofclaim 4 wherein the ammonium salt is selected from the group consistingof ammonium nitrate, ammonium sulfate and ammonium chloride, and saidacid is selected from the group consisting of acetic acid, hydrochloricacid and nitric acid.
 6. The process of claim 1 wherein M is selectedfrom the group consisting of iron, boron, chromium, aluminum andcombinations thereof.
 7. The process of claim 6 wherein thesilica/initial lattice metal oxide mole ratio is greater than about 100.8. The process of claim 1 wherein said crystalline composition has thestructure of ZSM-5, ZSM-11, ZSM-5/ZSM-11 intermediate, ZSM-20, ZSM-48,zeolite Y or zeolite Beta.
 9. The process of claim 1 wherein saidvolatile compound having a radius ratio of less than about 0.6 has acentral atom selected from the group consisting of Al⁺³, B⁺³, Be⁺²,Co⁺², Cr⁺⁶, Fe⁺³, Ga⁺³, Ta⁺⁵, Mn⁺⁴, Mo⁺⁶, P⁺³, Sb⁺³, Sn⁺⁴, Ti⁺⁴, V⁺⁵,W⁺⁶ and Zr⁺⁴.
 10. The process of claim 1 wherein said catalystcomposition further comprises a matrix material.
 11. The process ofclaim 10 wherein said matrix material comprises alumina.
 12. The processof claim 1 wherein said conversion conditions include a temperature offrom about 275° C. to about 600° C., a pressure of from about 0.5atmosphere to about 50 atmospheres and a liquid hourly space velocity offrom about 0.5 hr⁻¹ to about 100 hr⁻¹.
 13. The process of claim 1wherein said alcohol is methanol.
 14. A process for converting feedstockcomprising organic compounds selected from the group consisting ofalcohol, carbonyl, ether and mixtures thereof to conversion productcomprising hydrocarbon compounds which comprises contacting saidfeedstock at conversion conditions with a catalyst compositioncomprising a crystalline composition prepared by a method for enhancingthe catalytic activity of a porous inorganic crystalline compositioncomprising 98 mole percent or more SiO₂ and 2 mole percent or lessoxides of at least one initial lattice metal selected from those ofGroups IIIB, IVB, VB, VIB, VIIB, VIII, IIIA, IVA and VA of the PeriodicTable of the Elements and having an anhydrous anionic framework molarcomposition expressed by the formula

    (1-x)SiO.sub.2 :(x)MO.sub.n/2

wherein x is less than or equal to 0.02, M is said initial lattice metaland n is the valance of M, said crystalline composition having a totalcation exchange capacity of less than about 0.7 meq/gram, which methodcomprises the steps of calcining said crystalline composition at atemperature of from about 200° C. to about 600° C., contacting saidcalcined crystalline composition at a temperature of from about 100° C.to about 850° C. with a volatile compound comprising at least one metalto be tetrahedrally coordinated in the framework of said crystallinecomposition for a time sufficient to increase the total amount oftetrahedrally coordinated lattice metal in the framework of saidcrystalline composition whereby said total amount is greater than theamount of said initial lattice metal prior to said contacting, saidvolatile compound comprising said metal having a radius ratio of lessthan 0.6 and a size and shape which permits said volatile compound toenter the pores of said crystalline composition at the contactingtemperature and converting said volatile compound contacted crystallinecomposition to the hydrogen or hydronium form.
 15. The process of claim14 wherein said conversion to hydrogen or hydronium form comprisescalcining said volatile compound contacted crystalline composition at atemperature of from about 200° C. to about 600° C.
 16. The process ofclaim 14 wherein said conversion to hydrogen or hydronium form comprisescontacting said volatile compound contacted crystalline composition withan aqueous acid or ammonium salt solution and thereafter calcining saidmaterial at a temperature of from about 200° C. to about 600° C.
 17. Theprocess of claim 16 wherein said ammonium salt is selected from thegroup consisting of ammonium nitrate, ammonium sulfate and ammoniumchloride, and said acid is selected from the group consisting of aceticacid, hydrochloric acid and nitric acid.
 18. The process of claim 14wherein M is selected from the group consisting of iron, boron,chromium, aluminum, and combinations thereof.
 19. The process of claim18 wherein the silica/initial lattice metal oxide mole ratio is greaterthan about
 100. 20. The process of claim 14 wherein said crystallinecomposition has the structure of ZSM-5, ZSM-11, ZSM-5/ZSM-11intermediate, ZSM-20, ZSM-48, zeolite Y or zeolite Beta.
 21. The processof claim 14 wherein said volatile compound having a radius ratio of lessthan about 0.6 has a central atom selected from the group consisting ofAl⁺³, B⁺³, Be⁺², Co⁺², Cr⁺⁶, Fe⁺³, Ga⁺³, Ta⁺⁵, Mn⁺⁴, Mo⁺⁶, P⁺³, Sb⁺³,Sn⁺⁴, Ti⁺⁴, V⁺⁵, W⁺⁶ and Zr⁺⁴.
 22. The process of claim 14 wherein saidcatalyst composition further comprises a matrix material.
 23. Theprocess of claim 22 wherein said matrix material comprised aluminum. 24.The process of claim 14 wherein said conversion conditions include atemperature of from about 275° C. to about 600° C., a pressure of fromabout 0.5 atmosphere to about 50 atmospheres and a liquid hourly spacevelocity of from about 0.5 hr⁻¹ to about 100 hr⁻¹.
 25. The process ofclaim 14 wherein said alcohol is methanol.